The electrical properties of ferroelectric $\mathrm{Pb}(\mathrm{Zr},\mathrm{Ti}){\mathrm{O}}_{3}$ (PZT) and ferromagnetic $\mathrm{Co}{\mathrm{Fe}}_{2}{\mathrm{O}}_{4}$ (CFO) thin film multilayers (MLs) fabricated by pulsed laser deposition technique has been studied by impedance and modulus spectroscopy. The effect of various PZT/CFO configurations having three, five, and nine layers has been systematically investigated. The transmission electron microscopy images revealed that the ML structures were at least partially diffused near the interface. Diffraction patterns indicate clear PZT and CFO crystal structures in the interior and at the interface of the ML structure. Room temperature micro-Raman spectra indicate separate PZT and CFO phases in ML structure without any impurity phase. We studied frequency and temperature dependencies of impedance, electric modulus, and ac conductivity of ML thin films in the ranges of $100\phantom{\rule{0.3em}{0ex}}\mathrm{Hz}\char21{}1\phantom{\rule{0.3em}{0ex}}\mathrm{MHz}$ and $200\char21{}650\phantom{\rule{0.3em}{0ex}}\mathrm{K}$, respectively. We observed two distinct electrical responses in all the investigated ML films at low temperature $(l400\phantom{\rule{0.3em}{0ex}}\mathrm{K})$ and at elevated temperature $(g400\phantom{\rule{0.3em}{0ex}}\mathrm{K})$. We attributed these contributions to the grain effects at low temperature and grain boundary effects at high temperature. We explained this electrical behavior by Maxwell-Wagner-type contributions arising from the interfacial charge at the interface of the ML structure. Master modulus spectra indicate that the magnitude of grain boundary compared to grain becomes more prominent with the increase in the number of layer. The frequency dependent conductivity results well fitted with the double power law, $\ensuremath{\sigma}(\ensuremath{\omega})=\ensuremath{\sigma}(0)+{A}_{1}{\ensuremath{\omega}}^{{n}_{1}}+{A}_{2}{\ensuremath{\omega}}^{{n}_{2}}$, and the results showed evidence of three types of conduction process at elevated temperature: (i) low frequency $(l1\phantom{\rule{0.3em}{0ex}}\mathrm{kHz})$ conductivity is due to long-range ordering (frequency independent), (ii) midfrequency conductivity $(l10\phantom{\rule{0.3em}{0ex}}\mathrm{kHz})$ may be due to the short-range hopping, and (iii) high frequency $(l1\phantom{\rule{0.3em}{0ex}}\mathrm{MHz})$ conduction is due to the localized relaxation hopping mechanism.

Impedance spectroscopy of multiferroic Pb Zr x Ti 1 − x O 3 ∕ Co Fe 2 O 4 layered thin films

We have performed x-ray diffraction and Raman spectroscopy measurements in the temperature range of 300–873 K on a single phase epitaxially oriented BaTiO3 thin film grown by pulsed laser deposition on a single crystal MgO substrate. The θ–2θ room temperature diffraction measurements and asymmetric rocking curves indicate that the film is very weakly tetragonal with the c-axis parallel to the plane of the film. X-ray diffraction measurements up to high temperature reveal only a change in slope in the perpendicular to the plane lattice parameter around 450 K (in bulk Tc=395 K) indicating that a diffuse-like of phase transition is taking place. Room temperature polarized Raman spectra show that the film is indeed tetragonal with C4v symmetry and with the a-axis perpendicular to the film plane. Monitoring of the overdamped soft mode and the 308 cm−1 mode confirms that the phase transition is taking place over a wide temperature range according to the x-ray results. The increase of the phase transition temper...

Ferroelectric transition in an epitaxial barium titanate thin film: Raman spectroscopy and x-ray diffraction study

Barium titanate thin films have been prepared by chemical solution deposition on 18 μ m thick, industry standard copper foils in the absence of chemical barrier layers. The final embodiment exhibits randomly oriented BaTiO3 grains with diameters between 0.1 and 0.3 μ m, and an equiaxed morphology. The average film thickness is 0.6 μ m and the microstructure is free from secondary or interfacial phases. The BaTiO3 films are sintered in a high temperature reductive atmosphere such that copper oxidation is avoided. Subsequent lower-temperature, higher oxygen pressure anneals are used to minimize oxygen point defects. Permittivities of 2500 are observed at zero bias and room temperature, with permittivities greater than 3000 at the coercive field. Loss tangents under 1.5% are demonstrated at high fields. The BaTiO3 phase exhibits pronounced ferroelectric switching and coercive field values near 10 kV/cm. Temperature dependent measurements indicate a ferroelectric transition near 100∘C with very diffuse character. Combining the approaches of the multilayer capacitor industry with traditional solution processed thin films has allowed pure barium titanate to be integrated with copper. The high sintering temperature—as compared to typical film processing—provides for large grained films and properties consistent with well-prepared ceramics. Integrating BaTiO3 films on copper foil represents an important step towards high capacitance density embedded passive components and elimination of economic constraints imparted by traditional noble metallization.

Copper Compatible Barium Titanate Thin Films for Embedded Passives

Highly (100) textured graded manganese (Mn) doped Ba0.5Sr0.5TiO3 [BST (50/50)] thin films were deposited on lanthanum aluminate substrates using sol-gel technique. We have demonstrated that the graded acceptor doping is a promising technique to reduce the temperature coefficient of capacitance (TCC), loss tangent, and leakage current of BST thin films. In the temperature range between 175 and 260 K the reported TCC of Mn graded BST (50/50) films is less than 5.55×10−4/K, which is comparable to the best capacitors known so far. The lower temperature coefficient of the capacitance of the Mn graded films has been argued to be due to the induced compositional heterogeneity resulting into a distribution of the Curie temperature.

Improvement in electrical characteristics of graded manganese doped barium strontium titanate thin films

Single-phase perovskite 5 at. % Mn-doped and undoped polycrystalline BaTiO3 thin films have been grown under different oxygen partial pressures by pulsed laser deposition on platinum-coated sapphire substrates. Ferroelectricity is only observed for the Mn-doped and undoped BaTiO3 thin films grown under relatively high oxygen partial pressure. Compared to undoped BaTiO3, Mn-doped BaTiO3 reveals a low leakage current, increased dielectric loss, and a decreased dielectric constant. Ferromagnetism is seen on Mn-doped BaTiO3 thin films prepared under low oxygen partial pressure and is attributed to the formation of bound magnetic polarons (BMPs). This BMP formation is enhanced by oxygen vacancies. The present work confirms a theoretical work from C. Ederer and N. Spaldin on ferroelectric perovskites [Nature Mat. 3, 849 (2004)] that shows that the existence of ferroelectricity is incompatible with the existence of a spontaneous magnetization in Mn-doped BaTiO3 thin films.

Decisive role of oxygen vacancy in ferroelectric versus ferromagnetic Mn-doped BaTiO3 thin films

Ferroelectric thin films of barium titanate were fabricated by sol–gel technique on platinum substrates. The processing temperature was 700 °C. The films obtained with a thickness of 1.5 μm were dense, transparent, and showed ferroelectricity. Scanning electron microscopy and x-ray diffraction were used for studying the surface morphology and crystallographic structure of the film. Films in the metal–ferroelectric–metal configuration (MFM) were used for the electrical measurements. Dielectric constant and loss tangent were found to be 430 and 0.015, respectively, at 10 kHz under ambient conditions. The e′(T) curve shows broad peak centered around 120 °C as in the case of diffuse phase transition. The ac conductivity is proportional to ω0.9 in the low frequency region and ω1.8 in the high frequency region. The dc conductivity versus temperature curve showed a change in the slope around 125 °C, corresponding to the phase transition. To study the low temperature phase transitions, dielectric parameters on th...

Diffuse phase transitions, electrical conduction, and low temperature dielectric properties of sol–gel derived ferroelectric barium titanate thin films

S. Komarneni

Papers

Diffuse phase transitions, electrical conduction, and low temperature dielectric properties of sol–gel derived ferroelectric barium titanate thin films