Structure, microstructure and low-temperature dielectric properties of undoped SrTiO3 (STO) thin films prepared by sol–gel and deposited on Si/SiO2/TiO2/Pt substrates are studied. The effect of annealing temperature and of buffer layers on properties of STO films is analysed. Dielectric permittivity ε’, relative tunability nr and polarization P are lowest for STO films prepared without buffer layers and annealed at 750 °C and are highest for films prepared with buffer layers and annealed at 900 °C. The increase of c/a ratio for films with buffer layer and of the grain size for films annealed at higher temperature is used to explain the improved dielectric response. The dielectric permittivity of STO films prepared by low-cost sol–gel technique with optimized deposition conditions is found to be comparable to that of STO films fabricated by more sophisticated and expensive methods such as pulsed laser deposition.
A grain growth anomaly in Ti-rich strontium titanate ceramics is reported. Here we show that three discontinuities on the temperature dependence of grain growth take place with drops in the grain size at temperatures around 1500, 1550, and 1605 °C. We also show that similar discontinuities can be observed in the dependence of the grain boundary activation energy for conductivity and in the grain boundary thickness, assessed by impedance spectroscopy (IS). These notable coincidences are reported for the first time and strongly support the formation of different grain boundary complexions in polycrystalline oxides with transitions in between the observed grain growth regimens, which may be correlated to different grain boundary mobility and dielectric properties. These results call into question the discussion on the role of nonstoichiometry of SrTiO3 and complexions on the microstructure development and open opportunities to design properties of functional materials.
Solar energy is a major factor in the equation of energy, because of the unlimited potential of the sun that eclipses all other renewable sources of energy. Solar physical vapor deposition (SPVD) is a core innovative, original and environmentally friendly process to prepare nanocrystalline materials in a powder form. The principle of this process is to melt the material under concentrated solar radiation, which evaporates and condenses as nanopowders on a cold surface. We synthesized nanopowders of magnesium titanate by the SPVD process at PROMES Laboratory in Odeillo-Font Romeu, France. The SPVD system consists of a parabolic mirror concentrator, a mobile plane mirror (“heliostat”) tracking the sun and a solar reactor “heliotron”. The synthesized nanopowders were analyzed by X-ray diffraction (XRD) to know their crystalline structure and scanning electron microscopy (SEM) was used for determining the surface morphology. We have shown that the characteristics of obtained nanotitanates were determined by the targets’ composition and SPVD process parameters such as the working pressure inside the solar reactor and evaporation duration (process time).
Deliberately oxygen deficient potassium tantalate thin films were grown by RF magnetron sputtering on Si/SiO2/Ti/Pt substrates. Once they were structurally characterized, the effect of oxygen vacancies on their electric properties was addressed by measuring leakage currents, dielectric constant, electric polarization, and thermally stimulated depolarization currents. By using K2O rich KTaO3 targets and specific deposition conditions, KTaO3-δ oxygen deficient thin films with a K/Ta = 1 ratio were obtained. Room temperature X-ray diffraction patterns show that KTaO3-δ thin films are under a compressive strain of 2.3% relative to KTaO3 crystals. Leakage current results reveal the presence of a conductive mechanism, following the Poole-Frenkel formalism. Furthermore, dielectric, polarization, and depolarization current measurements yield the existence of a polarized state below Tpol ~ 367°C. A Cole-Cole dipolar relaxation was also ascertained apparently due to oxygen vacancies induced dipoles. After thermal annealing the films in an oxygen atmosphere at a temperature above Tpol, the aforementioned polarized state is suppressed, associated with a drastic oxygen vacancies reduction emerging from annealing process.
Due to the increasing availability of substitute materials for electrical porcelain, research is needed to adapt formulations involving these materials to the current economic realities of the industry. This study assessed the effect of iron oxide concentration (0, 1, 2, 3, 5, and 8 wt%) on the dielectric properties of an aluminous porcelain composition commonly employed for electrical insulation based on different values of temperature and frequency. Samples with iron oxide contents of 0, 3, and 5 wt% were analyzed using dilatometry, X-ray diffraction, and scanning electron microscopy to evaluate the thermal, structural, and microstructural changes related to their Fe2O3 concentrations. Both the dielectric constant (εr) and the loss tangent (tanδ) were measured and evaluated in every sample. Results indicated that the presence of Fe2O3 increased the dielectric constant and loss tangent, which could result in an increase in heating by dielectric losses. Fe2O3 contents of up to 5 wt% had no significant effect on the performance of these insulators at room temperature (~30 °C) and a high frequency (1 MHz), especially when the hematite phase was completely solubilized in the porcelain phases.
Constrained sintering of BaLa4Ti4O15 (BLT) thick films on flexible platinum foil and on rigid BLT substrate showed enhanced grain growth and anisotropic microstructure development when compared with bulk samples having similar green packing and sintered under the same conditions. The evolution of the microstructural parameters (grain and pore shape, orientation) during densification and their correlation was investigated in films and compared with the morphological evolution in bulk samples. It is then expected that the appropriate choice of substrate will allow designing tailored microstructures of functional thick films with optimized performance.
Poly(vinylidene fluoride)/Pb(Zr0.53Ti0.47)O3,([PVDF]1-x/[PZT]x) composites of volume fractions x and (0-3) type connectivity were prepared in the form of thin films. PZT powders with average grain sizes of 0.2, 0.84, and 2.35 μm in different volume fraction of PZT up to 40 % were mixed with the polymeric matrix. The influence of the inorganic particle size and its content on the thermal degradation properties of the composites was then investigated by means of thermo-gravimetric analysis. It is observed that filler size affects more than filler concentration the degradation temperature and activation energy of the polymer. In the same way and due to their larger specific area, smaller particles leave larger solid residuals after the polymer degradation. The polymer degradation mechanism is not significantly modified by the presence of the inorganic fillers. On the other hand, an inhibition effect occurs due to the presence of the fillers, affecting particularly the activation energy of the process.
The importance of electrophoretic deposition (EPD) is well recognized for thick film technology, but unfortunately there is no universal suspension medium for the EPD of oxides. Thus, the selection of the medium, the stability of the suspensions, and the control of the particle potentials, critical for a good deposition, need to be established for each new material being processed by EPD. In this article, we investigate the key parameters, studying the electrochemistry of BaNd2Ti5O14 (BNT) suspensions, and establish relationships between suspension media, EPD process conditions, microstructure of the deposits, and resulting electrical properties of the BNT films. Suspension stability of water, ethanol, acetic acid, and acetone-based media was analyzed in terms of zeta potential, particle size distribution, UV transmittance, and inductively coupled plasma spectrometry. The highest absolute zeta potential values determined for acetone with I2 and acetic acid media are in good agreement with the high stability, small and narrow particle size distribution, and low UV light transmittance measured for these suspensions. Very high quality thick deposits were consequently achieved. However, it was demonstrated that aging of the acetic acid-based suspension have serious negative effects on the EPD process for BNT materials, including leaching of the metallic elements with a consequent modification of the material stoichiometry, change of the conductivity of the suspension, and degradation of the films microstructure. These facts severely restrict the use of acetic acid. Our results clearly indicate that, besides the stability of the suspension, the electrochemistry and aging behavior are key aspects for the EPD of functional oxides. Our systematic approach could be viewed as providing a set of guidelines for the development of EPD of other oxides.
Carbon nanotubes (CNTs) have unique physical properties. This has been the driver for the current exploitation of their use in different advanced applications, such as in composite nanoscale devices. If a thermal treatment is required for the fabrication of the composite, the thermal decomposition behavior of the tubes is a key aspect in the integration process. Within this context, the thermal decomposition of multiwall CNTs (MWCNTs) under different conditions was studied in this work by DTA/TG, XRD, RAMAN spectroscopy and electron microscopy. Purified MWCNTs are stable up to 420 °C in air, as no weight loss occurs in TG/DTA analysis under non isothermal conditions but morphology changes were observed for isothermal conditions at 400 °C by Raman spectroscopy. In oxygen-rich atmosphere MWCNTs started to oxidized at 200 °C. However in argon-rich atmosphere and under a high heating rate MWCNTs remain stable up to 1300 °C with a minimum sublimation. The activation energy for the decomposition of MWCNTs in air was calculated to lie between 80 and 108 kJ/mol. These results have broad implications for the expanded use of MWCNTs in composites with functional complex oxides that usually require synthesis temperature above 650 °C.