In this work structural refinement, complex impedance spectroscopy, and Raman spectroscopy have been investigated on Na$_{0.5}$(Bi$_{1-x}$Dy$_x$)$_{0.5}$TiO$_3$ (xDyNBT) ceramic systems. The pure NBT, 2DyNBT and 5DyNBT compounds crystallize in a rhombohedral structure while the 15DyNBT composition crystallizes in an orthorhombic Pnma structure. We reported that dysprosium addition affects the phase transition temperatures as well as the dielectric losses. The electrical transport at high temperatures was investigated using the CIS over a wide frequency range. The studied samples showed a non-Debye type process, with a short-range relaxation for the pure NBT and a coexistence of both localized and long-range relaxations of charge carriers for the 2DyNBT and 5DyNBT compounds. For the high concentration, 15DyNBT, a short-range relaxation is observed. Moreover, using a brick-layer model we discuss the resistance and capacitance of the different contributors (grain and grain boundaries) in our samples. High temperature Raman spectroscopy investigation was performed in order to follow the temperature evolution of the structural transformations on ferroelectric compounds. Anomalies in the temperature evolution of the vibrational modes are seen to correlate well with the temperature transitions observed from dielectric measurements.
Observations by in-situ transmission electron microscopy (TEM) reveal the changes in domains morphology in 0.885(Bi1/2Na1/2)TiO3-0.05(Bi1/2K1/2)TiO3-0.015(Bi1/2Li1/2)TiO3-0.05BaTiO3 ceramics. Evolution of the macroscopic ferroelectric domains has been observed at 25 oC to 180 oC. The ferroelectric domains and their walls reduce progressively with increasing temperature. In the selected-area electron diffraction (SAED) patterns the crystallographic evidence of antiferroelectric domain is not found over the temperature range, which provides the evidence that the ferroelectric-antiferroelectric t…
NdFeO3 modified polycrystalline ceramics with composition (NdFeO3)0.1-(Ba0.7Sr0.3TiO3)0.9 (NFBST) ceramics have been synthesized via solid-state reaction route. The Rietveld refinement of the XRD data confirmed the existence of a tetragonal phase (P4mm) and a hexagonal phase (P63/mmc) in the prepared sample. The coexistence of phases has been also further confirmed from the Raman spectroscopy. The SEM image revealed dense microstructure with well packed grains of different sizes. At room temperature lossy P-E loop and weak ferromagnetism is observed in NFBST system. Complex impedance spectrosc…
Ferroelectric-like hysteresis loops of CaCu3Ti4O12 (CCTO) ceramic have been observed. We found that this unusual feature does not arise from the displacement of the Ti ions in the TiO6 octahedron, but apparently comes from the charges at the grain boundaries which consist of a CuO layer. The relaxation time of 2.9 milliseconds by the charges from the grain boundary, nearly corresponding to the inverse P - V sampling frequency of 1kHz, has been found in the impedance spectrum. According to the micro-Raman mapping, the CuO layer is found in the grain boundary and is perfectly distinguished from …
Dielectric permittivity was studied in ceramics of relaxor ferroelectric bismuth-sodium titanate Na$_{0.5}$Bi$_{0.5}$TiO$_{3}$. The measurements were performed on as sintered and heat treated in vacuum samples. The diffuse dielectric anomalies associated with the structural phase transitions were observed in as sintered samples. The intense peak of permittivity ($ \varepsilon_{\text{max}} \sim 10^{4}$) appeared after heat treating in vacuum. The anomaly of $\varepsilon(T)$ was contributed by slow polarization processes ($f<10$ kHz) and was non-stable, vanishing on heating in air up to $\sim 80…
Environmentally benign (1-x)Ba(Ti$_{0.8}$Zr$_{0.2}$)O$_3$-x(Ba$_{0.7}$Ca$_{0.3}$)TiO$_3$ (BZT-BCT) ceramics are promising materials due to their remarkable high piezoresponse [Liu and Ren, Phys. Rev. Lett. \textbf{103}, 257602 (2009)]. In this Letter, by focusing on local and average structure in combination with macroscopic electromechanical and dielectric measurements we demonstrate the structure property relationship in the tetragonal BZT-BCT ceramic. During high-temperature cubic to tetragonal phase transformation, polar nanoregions are manifested through the spontaneous volume ferroelectr…
Multiferroic bismuth ferrite Bi_2Fe_4O_9 (BFO) ceramic was synthesized by conventional solid state reaction route. X-ray diffraction and Rietveld refinement show formation of single phase ceramic with orthorhombic crystal structure (space group Pbam). The morphological study depicted a well-defined grain of size $\simeq$2μm. The optical studies were carried out by using UV-Vis spectrophotometer which shows a band gap of 1.53 eV and a green emission spectrum at 537 is observed in the Photoluminescence study. The frequency dependent dielectric study at various temperature revealed that the diele…
Dielectric behavior and conductivity mechanism in lead-free (100-x)(Li0.12Na0.88)NbO3-xBaTiO3 (0 to x to 40) piezoelectric ceramics were investigated using impedance spectroscopy over a wide temperature (-100 oC to500 oC) and frequency range (0.1 Hz to1 MHz). The grain and grain boundary response as well as the relaxation processes at different frequencies and temperatures were also discussed. A low frequency dispersion in dielectric permittivity (LFDD), a typical characteristic of high-temperature behavior was observed both below and above the ferro-paraelectric phase transition temperature, …
Structural, impedance, ferroelectric and magnetic properties were examined in multiferroic Bi_{2}Fe_{4(1-x)}Co_{4x}O_{9} (0$\leq$x$\leq$0.02) ceramics synthesized via solid-state reaction method. X-ray diffraction analysis and Rietveld refinement showed secondary phase formation (for x$\geq$0.01) which was subsequently confirmed from room temperature Raman spectroscopy study. The frequency dependence of impedance and electric modulus of the material showed the presence of non-Debye type relaxation in all the samples. The values of the activation energies calculated from imaginary impedance and…
Ba1-xMgx(Ti0.9Zr0.1)O3(x= 0.01 and 0.02) ceramics were prepared using the conventional solid state reaction. Rietveld refinement performed on X-ray diffraction patterns indicates that the samples are tetragonal crystal structure with P4mm space group. By increasing Mg content from 1 to 2% the unit cell volume decreased. Likewise, the grains size is greatly reduced from 10 to 4 micrometer. The temperature dependence of dielectric constants at different frequencies exhibited typical relaxor ferroelectric characteristic, with sensitive dependence in frequency and temperature for ac conductivity. …
Structural properties, impedance, dielectric and electric modulus spectra have been used to investigate the sintering temperature (Ts) effect on the single phase cubic spinel Ni0.6Zn0.4Fe2O4 (NZFO) ceramics synthesized by standard ceramic technique. Enhancement of dielectric constants is observed with increasing Ts. The collective contribution of n-type and p-type carriers yields a clear peak in notable unusual dielectric behavior is successfully explained by the Rezlescu model. The non-Debye type long range dielectric relaxation phenomena is explained by electric modulus formalism. Fast respo…
Magneli phase Ti5O9 ceramics with 200-nm grain-size were fabricated by hot-pressing nanopowders of titanium and anatase TiO2 at 1223 K. The thermoelectric properties of these ceramics were investigated from room temperature to 1076 K. We show that the experimental variation of the electrical conductivity with temperature follows a small-polaron model and that the Seebeck coefficient can be explained by a temperature-dependent Heikes-Chaikin-Beni model. The thermoelectric figure-of-merit ZT of this nanoceramic material reaches 0.3 at 1076 K.
The structural, dielectric and ferroelectric properties of lead-free (Na0.5-xKxBi0.5-xLax)TiO3 powders synthesized by sol-gel self-combustion method were investigated. Rietveld refinement of Synchrotron x-ray diffraction data confirms pure single phase rhombohedral crystal structure with R3c space group for all the compositions and anti-phase octahedral tilting angle decreased with increase in composition x. Homogeneity and elemental proportions were confirmed by Energy dispersive x-ray spectrometry. The temperature-dependent dielectric study has shown two diffuse type of dielectric anomaly fo…
We synthesized the pure and co-doped titanium dioxide (TiO$_2$) electrodes via spin coating. We examined the optical and electronic properties of as-prepared thin film electrodes with co-doping of transition metals and non-metals. The co-doping of Cu, Zn, and N increase the absorption of the radiation in the visible region. The doping leads to the formation of defect states in the electrodes. In this article, we have studied the carrier kinetics in pristine and co-doped TiO2 electrodes. To study the role of dopants in carrier transport of the synthesized TiO2 based electrodes, the electrochemi…
(1-x)Pb(Fe1/2Nb1/2)O3-PbTiO3(PFN-xPT)Ceramics with x = 0.13 sintered at 1473K show diffuse phase transition and very high dielectric constant at lower frequencies.The high value of dielectric constant at lower frequencies is shown to be due to the barrier layer formation.The resistivity of the PFN-xPT ceramics, obtained by complex impedance analysis, initially decreases with temperature and then shows an upward trend beyond the ferroelectric Curie point reminiscent of BaTiO3 based thermistors with PTCR effect.
CaCu3Ti4O12 (CCTO) ceramics are potential candidates for capacitor applications due to their large dielectric permittivity (e') values of up to 300 000. The underlying mechanism for the high e' is an internal barrier layer capacitor (IBLC) structure of insulating grain boundaries (GB) and conducting grain interiors (bulk). This behaviour is reviewed and discussed in detail. The origin of the IBLC structure is attributed to a small Cu non-stoichiometry in nominally insulating CaCu3Ti4O12, which varies between the GBs and bulk. Such non-stoichiometry effects are studied in detail by analyzing bu…
CaCu3Ti4O12 (CCTO) ceramics which has perovskite structure gained considerable attention due to its giant permittivity. But, it has high tan δ (0.1 at 1kHz) at room temperature, which needs to be minimised to the level of practical applications. Hence, TeO2 which is a good glass former has been deliberately added to CCTO nano ceramic (derived from the oxalate precursor route) to explore the possibility of reducing the dielectric loss while maintaining the high permittivity. The structural, morphological and dielectric properties of the pure CCTO and TeO2 added ceramics were studied using X-ray…
The solid solution 0.5Ba(Ti0.8Zr0.2)O3-0.5(Ba0.7Ca0.3)TiO3 (BCZT) is a promising lead-free piezoelectric material with exceptionally high piezoelectric coefficients. The strong response is related to structural instabilities close to ambient temperature. We report here on temperature-induced anomalies in the dielectric, piezoelectric, and elastic coefficients and Raman spectroscopy of ceramic BCZT. The data indicate ferroelectric-ferroelectric structural phase transitions in this material in addition to those previously reported. An anomaly is also observed above the Curie temperature TC and i…
The charge transport mechanism and the macroscopic dielectric constant in polycrystalline device materials commonly exhibit several components such as electrode-sample interface, grain boundary and bulk contributions. In order to gain precise understanding of the functionality of polycrystalline electroceramic device materials it is essential to deconvolute these contributions. The paradigm of functional thermistor ceramics based on thick film spinel manganates has been studied by temperature dependent alternating current impedance spectroscopy. Three typical relaxation phenomena were detected…
An impedance spectroscopy (IS) is a versatile tool to study the effect of grains (bulk), grain boundaries and electrode-electrolyte interface on dielectric and electrical properties of electro-ceramics. This study only focuses the high frequency (1 kHz to 10 MHz) probe of bulk ferroelectric capacitance near ferroelectric phase transition temperature (FPTT). The PZTFW single phase and PZTFW-CFO composites, respectively, have been investigated to understand the microstructure-property relation. Keeping in mind the complex microstructure of both systems, low frequency ( less than 1 kHZ ) impedanc…
Ferroelectric glass-ceramics are promising composite materials with dual properties, of high dielectric permittivity and high dielectric breakdown strength. In this context, new phosphate glass-ceramics 2BaO-0.5Na2O 2.5[(1-x)Nb2O5 xWO3]-1P2O5 (x=0, 0.1, 0.2, 0.3 and 0.4) designated as B0, B1, B2, B3, B4 respectively, were prepared by the controlled crystallization technology and then crystallized at high temperature of 760 °C for 10 hours. Subsequently, the obtained glass-ceramics were studied by Differential Scanning Calorimetry (DSC), X-ray powder diffraction (XRD), Raman, impedance spectros…
We have investigated the structural and dielectric properties of Sr$_{2}$TiO$_{4}$,the first member of the Sr$_{n+1}$Ti$_{n}$O$_{3n+1}$ Ruddlesden-Popper series, within density functional theory. Motivated by recent work in which thin films of Sr$_{2}$TiO$_{4}$ were grown by molecular beam epitaxy (MBE) on SrTiO$_{3}$ substrates, the in-plane lattice parameter was fixed to the theoretically optimized lattice constant of cubic SrTiO$_{3}$ (n=$\infty$), while the out-of-plane lattice parameter and the internal structural parameters were relaxed. The fully relaxed structure was also investigated.…
Ultra-high-temperature ceramics (UHTCs) are optimal structural materials for applications that require extreme temperature resilience, resistance to chemically aggressive environments, wear, and mechanical stress. Processing UHTCs with laser-based additive manufacturing (AM) has not been fully realized due to a variety of obstacles. In this work, selective laser reaction sintering (SLRS) techniques were investigated for the production of near net-shape UHTC ceramics such as HfC, ZrC, TiC, HfN, ZrN, and TiN. Group IV transition metal and metal oxide precursor materials were chemically converted…
Representation of dielectric properties by impedance spectroscopy (IS) is analyzed carefully in this paper. It is found that IS is not a good tool to describe a uniform system because a pseudo relaxation peaks exists at low frequency limit corresponding to direct current (DC) conductivity and two relaxation peaks appears simultaneously corresponding to one relaxation process for a high loss system with tand>1. However it is very convenient to describe a multiple phase system with IS. When dielectric properties are shown by Cole-Cole equation, only one Cole-Cole arc appears for one phase in IS,…
History-dependent and frequency-dependent dielectric nonlinearities induced by polar nanoregions in a thin film of 0.5 ( Ba 0.7 Ca 0.3 TiO 3 ) -- 0.5 ( BaZr 0.2 Ti 0.8 O 3 )
The solid solution $0.5Ba(Ti_{0.8}Zr_{0.2})O_3$-$0.5(Ba_{0.7}Ca_{0.3})TiO_3$ (BCZT) has become a promising member of the lead-free piezoelectric materials because of its exceptionally high piezoelectric properties. In this study, we focus on studying pressure-dependent Raman spectroscopy, powder x-ray diffraction and dielectric constant measurements on BCZT. The data show several structural transitions are present, where the system from ambient mixed phase (tetragonal, {\it {P4mm}}+ orthorhombic {\it {Amm2}}) transforms into single phase ({\it {P4mm}}) at 0.26 GPa, then converts into cubic pha…
We introduce an equivalent-circuit element based on the theory of interface pinning in random systems, to analyze the contribution of domain wall motion below the coercive field to the impedance of a ferroelectric, as a function of amplitude $E_0$ and frequency $f$ of an applied ac electric field. We investigate capacitor stacks, containing ferroelectric 0.5(Ba$_{0.7}$Ca$_{0.3}$)TiO$_{3}$--0.5Ba(Zr$_{0.2}$Ti$_{0.8}$)O$_{3}$ (BCZT) thin films, epitaxially grown by pulsed laser deposition on Nb-doped SrTiO$_3$ single crystal substrates and covered with Au electrodes. Impedance spectra from $f=10…
This work concerns glasses belonging to SiO2-Al2O3-CaO-ZrO2-TiO2-Nd2O3 system that lead to zirconolite crystallization in their bulk after nucleation + crystal growth thermal treatments and that could find application as nuclear waste form. The understanding of crystallization processes in glasses implied to investigate their structure. The environment around Ti, Zr (nucleating agents) and Nd was characterized for various Nd2O3 loadings. Electron spin resonance study of the small amount of Ti3+ occurring in glasses enabled to identify two types of sites for titanium. EXAFS showed that Zr occup…
The work presents the investigations of Li1.3Al0.3Ti1.7(PO4)3-xLiF Li-ion conducting ceramics with 0 < x < 0.3 by means of X-ray diffractometry (XRD), 7Li, 19F, 27Al and 31P Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR) spectroscopy, thermogravimetry (TG), scanning electron microscopy (SEM), impedance spectroscopy (IS) and density method. It has been shown that the total ionic conductivity of both as-prepared and ceramic Li1.3Al0.3Ti1.7(PO4)3 is low due to a grain boundary phase exhibiting high electrical resistance. This phase consists mainly of berlinite crystalline phase as well…
The possibility of obtaining relatively high dielectric constant polymer-ceramic composite by incorporating the giant dielectric constant material, CaCu3Ti4O12 (CCTO) in a Poly(vinylidene fluoride) (PVDF) polymer matrix by melt mixing and hot pressing process was demonstrated. The structure, morphology and dielectric properties of the composites were characterized using X ray diffraction, Thermal analysis, Scanning Electron Microscope, and Impedance analyzer. The effective dielectric constant of the composite increased with increase in the volume fraction of CCTO at all the frequencies (100 Hz…
We report on the synthesis of complex lead-free perovskite-type (1-x)(Ba$_{0.8}$Ca$_{0.2}$)TiO$_3$-xBi(Mg$_{0.75}$W$_{0.25}$)O$_3$ (BCT-xBMW) and (1-x)(Ba$_{0.8}$Ca$_{0.2}$)TiO$_3$-xBi(Mg$_{0.75}$Mo$_{0.25}$)O$_3$ (BCT-xBMM) solid solutions via conventional solid-state reaction route. The sintering temperature was adjusted as a function of composition x to obtain dense samples (relative densities over 95%) at the same time minimizing bismuth evaporation. X-ray diffraction analysis shows formation of single-phase perovskites for $0 \le x \le 0.10$ in the BCT-xBMW series and increasing concentra…
In this paper, we reported the effect of Cu doping on the structural and dielectric properties of Ba$_2$Y$_{1-x}$Cu$_x$TaO$_{6-y}$ (0.00 $\leq$ x $\leq$ 0.50) ceramics at room temperature. The Copper for Yttrium substitution reduces the sintering temperature and leads to structural changes in the Ba$_2$YTaO$_6$ rock-salt crystalline structure. Dielectric permittivity and complex impedance spectroscopy measurements suggested enhancement of the dielectric constant and occurrence of interfacial Maxwell-Wagner polarization.
Processing-Controlled Structural Uniformity and Oxide-Ion Conduction in Na0.52Bi0.47TiO3 Ceramics Probed by Eu3+ Photoluminescence
State Key Laboratory of Integrated Optoelectronics, Key Laboratory of UV Light-Emitting Materials and Technology of Ministry of Education, School of Physics, Northeast Normal University（集成光电子学国家重点实验室，教育部紫外发光材料与技术重点实验室，物理学院，东北师范大学）
Temperature dependent conductivity, dielectric relaxation, electrical modulus and impedance spectroscopy of Ni substituted Na$_{3+2x}$Zr$_{2-x}$Ni$_{x}$Si$_2$PO$_{\rm 12}$
The BaCe0.8Y0.2O3-δ proton conductor under hydration and under compressive strain has been analyzed with high pressure Raman spectroscopy and high pressure x-ray diffraction. The pressure dependent variation of the Ag and B2g bending modes from the O-Ce-O unit is suppressed when the proton conductor is hydrated, affecting directly the proton transfer by locally changing the electron density of the oxygen ions. Compressive strain causes a hardening of the Ce-O stretching bond. The activation barrier for proton conductivity is raised, in line with recent findings using high pressure and high tem…
Crystalline Bi5NbO10 nanoparticles have been achieved through a modified sol-gel process using a mixture of ethylenediamine and ethanolamine as a solvent. The Bi5NbO10 nanoparticles were characterized by X-ray diffraction (XRD), differential scanning calorimetry/thermogravimetry, fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM) and Raman spectroscopy. The results showed that well-dispersed 5-60 nm Bi5NbO10 nanoparticles were prepared through heat-treating the precursor at 650C and the high density pellets were obtained at temperatures lower than those com…
